Flame resistant polyester resinous compositions containing combined halogens and phosphorous and certain alkaline earth metal salts and the process of preparing the same



United States Patent 1. 2,822,340 FLAME RESISTANT POLYESTER RESINOUS COM- POSITIONS CONTAINING COMBINED HALO- GENS AND PHOSPl-IOROUS AND CERTAIN ALKALINE EARTH METAL SALTS AND THE PROCESS OF PREPARING THE SAME John David McGovern, Norwalk, Conn., and George Bliss Duhnkrack, Harrison, N. Y., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application October. 12, 1955 Serial No. 549,173 15' Claims. (Cl. 26022) This invention relates to a clear, light and heat stabilized flame-resistant, self-extinguishing resinous composition. Further, this invention relates to a lightandzheat=stable flame-resistant, self-extinguishingresinous composition, .its method of production and products produced-therefrom.

The productionof flame-resistant resinous compositions is desired, inasmuch assaid compositionsfind many uses, as for example, in molded and laminated articles as in decorative and structural applications. Resinous compositions also find many uses in certain instances where other materials cannot be used. It is readily apparent, therefore, that a fiameand heatand Weather-resistant resinous composition is desirable and would find immediate employment in the art. Since resinous compositions are primarily hydrocarbon.materials, they are oftenreadily flammable. They are, furthermore, subject to discoloration from exposure to the atmosphere. Therefore, many attempts have been made to produce stable resinous compositions that are both flame resistant and stable against becoming discolored-from heat, light, moisture, etc., to which these compositions may be exposed.

We have found that resinous compositions whichncontain halogens, to impart flame-resistance, have a. tendency to discolor badlyfrom heat and from weathering conditions of the exposed atmosphere. Obviously,.whenv the material is employed in an internal or hidden application not exposed to view, it is not important that the material be free from these discoloring efiects. However, when the material finds use, as for example, in transparent and trans lucent application Where appearance is paramount, such as in corrugated glass-filled structural pieces for walls and ceilings, it is desired that the material be water=clear when produced and also that the material retain this clearness after prolonged exposure tomoisture, heat, sunlight, etc; We have found that the resistance to discoloration ofthe resinous compositions according to the teachings of our invention is greatly improved by the addition thereto of a small amount of salt or mixture thereof,.selectedfromthe alkaline metal salts of fatty acids containing from 8 to 20 carbon atoms.

The resinous compositions prepared in accordance with our invention are polymerizable unsaturated polyesterresinous materials. Further, the resinouscompositions-pre pared in accordance with our invention are-polymerizable unsaturated resinous materials which are copolymer-izable with a compoundcontaining a polymerizable CH =C group and having a boiling point:ofat\least.60. C.

It is an object: of our invention to produce a clear weatherand flame-resistant, self-extinguishing polyester resinous composition. It is a further and more specific object of our invention to produce a heat-, light-,. and weather-stable, flame-resistant unsaturated polyester. resinous composition that may be polymerized with a compound containing a polymerizable CH=C group. These and other objects of my -invention will be discussed morefully hereinbelow.

As is well known in the art, conventionaiipoiymerizable unsaturated polyesterresins, such-as thoseprepared byre acting an ethylenically unsaturated 'polycarboxyliw acid "ice with a polyhydric aliphatic alcohol in admixture with a polymerizable compound containing a polymerizable CH =C .group, are extremely usefulasresinou's compositions, particularly in thefield'ofmolding, casting and laminating. These compositions, generally speaking, are not fire-resistantas such; Inorderto obtain a-fire-resistant material, it has been necessary to introducephysica'lly other compounds into the composition. In a cop'ending application by-Lennart A; Lundberg, Serial- No; 360,839, filed June 10, 1953, a flame-resistant, self-extinguishing light-stable polyester resinous composition and method of making is disclosed. Inthe composition therein disclosed fire-resistance depends oncombining inthe polyester resins sutficient amountsof halogenated reactantsto provide from about 5 to 50% by weightof chlorine, bromine, and iodine in the form of halogenated polyhydric alcohols or halogenated polycarboxylic acids together withalkyl phosphates as hereinafter more fully described. The halogens'employed'are those'ha-ving anatomic weight greater than'-3 5,-namely'chlorine, bromine, and iodine. Light stability is found to depend upon incorporating in the polyester fromabout 0.01% to about 5%,- preferably from 0.1% tO'2r% byW6lght based on the total weight of polyester-monomer composition of a benzophenone compound-having; the formula (SH Y wherein R is an alkyl group havingbetween l'and'4 carbon atoms, X is an alkyl groupcontaihing between 1 and 4 carbon atoms or an alkoxyggroup containingbetween 1 and 4 carbon atoms, orhydrog'en or halogen group, and Y is an alkyl group containing between'l and 4 carbon atoms or an alkoxy group containing between 1 and 4 carbon atoms'or hydrogen or" a halogen group or a hydroxyl group based on thetotal Weight of the polyester resin solids and the weight oftlie'rnonomeric material containing the:polymerizableCH=C groupmay be added.

The preparation of the polymerizableunsaturated-polyester resins utilizing halogenated polyca'r'boxylic acidsand polyhydric" alcohols is carried out exactly-as if the reactants were unhalogenated; In the preparation of' the polymerizable unsaturated polyester resinous compositions ofthe present invention,-.one may make use'of the ethylenically unsaturated polycarboxylic acidsysuch as maleic, fumaric, aconitic, itaconic, andth e'lile'i The ethylenica-lly unsaturated polycarboxylic acids include those known as the alpha, beta. unsaturated-acids. These unsaturated acids should be present in' aii- -a'mo'unt approximating at-least 20% by weight of-thetotallwei'ght of the polycarboxylic acids usedand" preferably in amounts varying between about 25 and"6'5 by weight based on the-total weight of polycarhoxylicacid present. If. it is desired to make use of polycarboxylic-acids, which are free of nonbenzenoid uusaturation, one-could use such' acidsa's phthalic, malonic, succinic, .glut'ari'c, seb'acie, and the like, but in amounts correspondingly" in proportion'. to; the totalamount of pjolycarboxylioacid present. Wheneveravailable, the anhydrides 'ofdhes'e acids maybe used, c. g., maleic anhydride,:phtha'1icranhydiidepand as used herein, po1ycarboxylic acids. includef thepolycarboxylic 'anhydrides. when available. Also, mixtures of the acids and anhydrides may-beuseddnth'e preparation of the polyester resin. Illustrative examples of halogenated polycarboxylic acids and anhydr'idesz thereof.that may be used in our invention'areZbromofumarioacid, chlorofumaric acid,bromomaleicaacid, .chlorom'aleic acid; dibromomaleicacid; chloromaleica'nhydri'de, dibror'nm maleic anhydride, dichloromaleic anhydride, bromomalonic acid, chloromalonic acid, dibromomalonic acid, bromosuccinic acid, alpha, beta-dibromosuccinic acid, alpha, beta-diiodosuccinic acid, alpha, beta-dichlorosuccinic acid, alpha, beta-dichlorosuccinic anhydride, 3-bromophthalic acid; 4-chlorophthalic acid; 3,4-dibromophthalic acid; 3,6-dichlorophthalic acid; tetrachlorophthalic acid; B-bromophthalic anhydride; 4-chlorophthalic anhydride; 3,6-dibromophthalic anhydride; 3,6- dichlorophthalic anhydride; 4,5-dichlorophthalic anhydride; tetrachlorophthalic anhydride, dibromosebacic acid; hexachloroendomethylene tetrahydrophthalic acid; hexachloroendomethylene tetrahydrophthalic anhydride and the like. a

As polyhydric alcohols which may be used in the preparation of the polymerizableunsaturated polyesters of the present invention, it is preferred that those alcohols containing only two hydroxy groups be used. However, those alcohols containing three, four, or more hydroxy groups may be used in minor amounts. Illustrative examples of the various dihydroxy alcohols that find employmeut in our invention are: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanedioll,4-butanediol-l,3, butanediol-1,2, pentanediol-1,4, pent'anediol-LS, hexanediol-1,6, and the like. Polyglycols, such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and the like may be employed. Polyhydric alcohols, as glycerol, pentacrythritol, dipentaerythritol, and the like may also be used in our invention.

Illustrative examples of halogenated polyhydric alcohols that may beused in our invention are 3,4-dibromo-3- chloro-1,2-butanediol; 2,3-dibromo-l,4-butanediol; 1,4-dichloro-2,3-butanediol; l,4-diiodo-2,3-butanediol; S-chloro- 1,2-pentanediol; l,5,5,5-tetrachloro-1,3-pentanediol; chloro- 1,5-pentanediol and the like.

Illustrative of the benzophenone compounds of the general formula which may be employed to impart light stability to the reaction product are such as 2-hydroxy- 4-methoxybenzophenone; 2,2-dihydroxy-4,4'-dimethoxybenzophenone; 2,2 dihydroxy 4,4 diethoxybenzophenone; 2,2'-dihydroxy-4,4-dibutoxybenzophenone; 2,2 dihydroxy-4-methoxy-4'-ethoxybenzophenone; 2,2-dihydroxy-4-methoxy 4' propoxybenzophenone; 2,2 dihydroxy-4-methoxy-4'-butoxybenzophenone; 2,2'-dihydroxy- 4-ethoxy-4-propoxybnzophenone; 2,2'-dihydroxy-4-ethoxy-4-butoxybenzophenone; 2,3-dihydroxy-4,4'-dimethoxybenzophenone; 2,3'-dihydroxy-4-rnethoxy-4'-butoxybenzophenone; 2 hydroxy-4,4,5'-trimethoxy benzophenone; 2 hydroxy-4,4',6-tributoxybenzophenone; 2 hy drxy-4butoxy-4,5'-dimethoxybenzophenone; 2-hydroxy- 4-ethoxy-2'4'-dibutylbenzophenone; 2-hydroxy-4-propoxy- 4',6'-dichlorobenzophenone; 2-hydroxy-4-propoxy-4'6-dibromobenzophenone; 2-hydroxy-4-ethoxy-benzophenone, 2-hydroxy-4-propoxybenzophenone, 2-hydroxy-4-butoxybenzophenone, 2-hydroxy 4 methoxy-4-methylbenzo-. phenone, 2-hydroxy-4-methoxy-4'-ethylbenzophenone, 2- hydroxy-4-methoxy-4-propylbenzophenone, 2-hydroxy-4- methoxy-4-butylbenzophenone, 2-hydroxy-4-methoxy-4'- chlorobenzophenone, 2-hydroxy-4-methoxy-4-bromobenzophenone, 2-hydroxy-4,4-dimethoxybenzophenone, 2-hydroxy-4,4'-dimethoxy-3-methylbenzophenone, 2-hydroxy- 4,4'-dimethoxy-2-ethylbenzophenone, 2-hydroxy--'-l,4',5'-v trimethoxybenzophenone, 2-hydroxy-4-ethoxy-4 methylbenzophenone, 2-hydroxy-4-ethoxy-4-ethylbenzophenone, 2-hydroxy-4-ethoxy-4'-propylbenzophenone, 2-hydroxy-4- ethoxy -'4 butylbenzophenone, 2 hydroxy-4-ethoxy-4'-' methoxybenzophenone, 2 hydroxy 4,4 diethoxybenzo-f phenone, 2-hydroxy-4-ethoxy-4'-propoxybenzophenone, 2- hydroxy-4-ethoxy-4'-butoxybenzophenone, 2 hydroxy-4- ethoxy-4'-chlorobenzophenone, Z-hydroxy 4 ethoxy-4-. bromobenzophenone, and the like. From this illustrationof compounds which are representative of the class which maybe used in the invention in the present application,

there may be used as substituents in the 2, 3', 4', 5',

and 16'v position, either methyl, ethyl, propyl, or butyl,

4 or methoxy, ethoxy, propoxy, or butoxy, or any of the halo groups, namely chloro, bromo, or iodo.

In the preparation of the polymerizable unsaturated polyesters, one may use the polyhydric alcohols and the polycarboxylic acids in a proportion substantially mol for mol and preferably an excess of alcohol approximating above the stoichiometric quantity required for complete esterification. If polyhydric alcohols containing more than two hydroxy groups are used, calculation of the molar proportion should be made on a stoichiometric basis so as to make allowance for the additional hydroxy groups, such as those found in glycerol, pentaerythritol, and the like. This is also true when polycarboxylic acids having more than two carboxyl groups are employed. A sufiicient quantity of the alcohol and acid should be reacted so as to produce an ultimate polyester resinous material having an acid number not greater than about 55 and not lower than about 20 and preferably an acid number from about 35 to 40. The combined halogen content of the polyester resins should be from about 5% to about 50% and preferably from about 25% to 35% by weight.

The polymerizable unsaturated polyesters are admixed with a monomeric compound containing the polymerizable CH =C group to give a composition that may be cured to a stable thermoset condition. One may use about 10 parts by weight of the monomeric material to about parts of the unsaturated polyester resin up to about 50 parts of the monomeric material to about 50 parts of the polymerizable unsaturated polyester resin. The preferred embodiment however, is to use from about 25 parts of the monomeric material to about 35 parts of the monomeric material with about 75 parts to about 65 parts of the polymerizable unsaturated polyester resin.

The monomeric material containing the polymerizable CH =C group has a boiling point of at least 60 C. among the polymerizable monomeric materials that may find use in our. invention are such as styrene, side-chain alkyl and halo-substituted styrenes, such as alpha methylstyrene, alpha chlorostyrene, alpha ethylstyrene, and the like, or alkyl and halo ring-substituted styrene, such as ortho, meta and para-alkylstyrenes, such as o-methylstyrene, p-ethylstyrene, meta-propylstyrene, 2,4-dimethylstyrene, 2,5-diethylstyrene, the ortho-, mcta-, and parabromostyrenes and chlorostyrenes, dibromostyrenes, dichlorostyrenes, and the like. Still further, one can make use of the allyl compounds, such as diallyl phthalate, tetrachlorodiallyl phthalate, allyl alcohol, methallyl alcohol, allyl acetate, allyl methacrylate, diallyl carbonate, allyl lactate, allyl alphahydroxyisobutyrate, allyl trichloro silane, allyl acrylate, diallyl malonate, diallyl oxalate, allyl gluconatc, allyl methylgluconate, diallyl adipate, diallyl sebacate, diallyl citraconate, the diallyl ester of muconic acid, diallyl itaconate, diallyl chlorophthalate, diallyl dichlorosilane, the diallyl ester of endomethylene tetrahydrophthalic anhydride, the diallyl ester of tetrachloro endomethylene tetrahydrophthalic anhydride, triallyl tricarballylate, triallyl aconitate, triallyl cyanurate, triallyl citrate, triallyl phosphate, trirnethallyl phosphate, tetraallyl silane, tetraallyl silicate, hexallyl disiloxane, and the like.

To render tire-resistance to the composition of the present invention, it is necessary that alkyl phosphates be coreactcd with the polycarboxylic acid and polyhydric alcohol in amounts suflicient to provide from about 0.1% to about 5% of combined phosphorus, preferably from about 0.5% to about 1.5% by weight based on the total weight of the polyester, during the preparation of the polymerizable unsaturated polyester resin, as distinguished from the introduction of phosphorus-containing materials into the polyester resin after the latter had been produced. Post-addition of phosphorus does not impart fire-resistance and the fact that the latter is only a physical mixture is shown by loss in weight of the ma:

terial when it is subjected to prolonged -elevated* tem'- peratures.

The present invention deals with polyester resins wherein the alkyl phosphates are chemically combined therein. This is evidenced by the fact that there is no significant Weight loss when the resinous materialsare' exposed at elevated temperatures for long periods. Examples-of-th'e alkyl phosphates that may be utilized in the process of our invention are those in which the alkyl group contains from 1 to-4 carbon atoms. Illustrative examples of such compounds are triethyl phosphate, diethyl phosphate, monoethyl phosphate, and the like. Thealkyl group has been set forth as the ethyl radical, but it will be understood that the alkyl group may-be such as methylj'propyl, butyl, isopropyl, isobutyl, tertiarybutyl, and the like. The amount of alkyl phosphate reacted is such that the polyester contains from about 0.1% to about 5% of combined phosphorus, preferably from about 0.5% to about 1.5% by weight based on the total weight.

Upon combining halogenated and phosphorus compounds into the resinous composition to impart fireresistance thereto, it has been found that considerable discoloration occurs when the cured composition is exposed to moisture, heat, and sunlight. We have found that the major factor in causing discoloration of fireresistant resins is heat, although moisture and light-also contribute in discoloring these materials. Discoloration, browning, or clouding of these compositions has seriously limited the application of these materials for structural and decorative uses, particularly in the glass-filled corrugated and flat sheeting often employed as wall and-ceiling components in buildings.

We have found that the incorporation of an alkaline earth metal salt of a fatty acid having from 8 to 20 carbon atoms imparts remarkable resistance to discoloration Without in the least diminishing the fire-resistant characteristic of these resinous materials. The alkaline earth metals contemplated are barium, cadmium, magnesium, and strontium. Marked resistance to discoloration is apparent when amounts from as little as 0.1% and less up to about 10% of these alkaline earth metal salts of fatty acids having 8 to carbon atoms-are used. Examples of such compounds include salts of the saturated fatty acids, caprylic, pelargonic, capric, undecylic,.lauric, tridecanoic, myristic, pentadecanoic, palmitic, margonic, stearic, nondecylic, and arachidic; the olefine acids, such as hypogaeic, oleic, and the like; and those acids containing a triple bond, such as palmitolic, stearolic, and the like. Preferred results are obtained when these salts in amounts of from 1% to 5% by weight based on the total weight of the resinous composition are employed.

In the formulation of the resinous composition of our invention, it is necessary that a catalyst be present to effect the polymerization of the unsaturated polyester resin and the monomeric material containing the polymerizable CH C group. It is preferred, as is well known in the art, that a catalyst of the peroxide class be utilized. The amount of the catalyst may vary over rather wide limits, depending upon the desired rate of polymerization of the material. Thus, from about 0.1% to about 10% by weight based on the total weight of the polymerizable composition may be used. Preferably, from about 0.5% to about 1% by weight of the catalyst based on the total weight of the polymerizable resinous composition gives the desired results. It isobvious that otherproportions of the catalyst may be utilized when a faster or slower rate of cure is desired. Examples of the organic peroxide catalyst that may be used in our invention are such. as benzoyl peroxide, succinyl peroxide, lauroyl peroxide, acetyl peroxide, perbenzoic acid, peracetic acid, anisoyl peroxide, toluyl peroxide, p-bromobenzoyl peroxide, furoyl peroxide,.and chloracetyl peroxide; hydroperoxides, such as cumene hydroperoxide, tertiary .butylhydroperoxide, and the like; or any organic ozonide, such-as-diisopropyleneozonide, diisobutylene ozonide, or a mixture of such substances, may be used as the curing catalyst.

If it is desired to efliect lowtemperature cure of the unsaturated polyester resinous composition, it will be desirable to make use of a material commonly referred to as a promoter. These promoters, such as the mercaptans, the alkyl substituted anilines, and the metallic salt dfiers, e. g., cobaltnaphthalate are generally dispersed in a solution of a suitable solvent material, such as the monomeric polymerizable material. If high temperature cure is to be accomplished, apromoter is not necessary. Promoters which are useful 'in this connection have been disclosed in prior art as represented'by such patents as U. S. 2,466,800 and 2,480,928.

In order to inhibit premature cure during handling and/ or shipping and also to control the rate of polymerization during the cure of the resinous composition of our invention, it isadvantageous to add amoderate amount of an-inhibiting agentto the resinous composition. The amount of .inhibitingagent used is that required to give the desired degree of inhibiting effect. Examples of inhibiting agents that'may be used in our invention are quinone, naphthaquinone, hydroquinone, ditertiary butyl hydroquinone, ditertiary butyl paracersol, pyrogallol, catechol, tertiary butyl catechol, ,2,2-methylene bis (4- methyI-G-tertiary butyl phenol), dinitroortho cresol, pamino phenol HCl, butylated hydroxy anisole,"monobutyl meta cresol, tannic acid, and the like, and aromatic amines, such as aniline or phenylene diamine. Mixtures of the inhibiting agents may also be used, if desired. About 0.008% of inhibiting agent by weight based on the total Weight of the resinous composition usually gives satisfactory results.

In order to demonstrate the self-extinguishing properties .of the material, the following standard underwriters test was carried out:

A l-inch by 9-inch glass-filled laminate is exposed to a 5-inch flame froma Bunsen burner, the tip'of'the' inner flame being 1 inch long. The flame is exposed at an angle of 45 to the laminate one inch from its bottom for seconds. The flame is then removed and the time required for the flame to extinguish itself is-recorded. The flame, in the burning of the material, must extinguish itself in 20 seconds to be acceptable.

The standard burning rate as set forth by the specifications of ASTM D757-49 was also carried. out. The specifications for this test are:

An igniting bar is heated to 950 C. byalternating or direct current, the electrical input of which is adjusted to 350:20 Watts. A test specimen 5 inches by /2 inch by A3 inch is clamped in a holder with its length horizontaland at right angle to the axis of the igniting:bar and its width in a vertical plane. The length of the'specimen free to burn is 4 inches. The front. endof the specimen is brought into contact with the ignitingbar andallowed to remain in this position for 3 minutes. After 3 minutes, any flaming shall be extinguished, the specimen removed, and the length burned measured. The length burned divided by 3 then gives the burning rate in inchesper minute.

The self-extinguishing test as setforth in the ASTM specifications D635-44 was also carried out. The specifications for this test are:

A test specimen 6 inches in length by /2 inch inwidth and of the thickness of .the material as normally used is clamped in a support with its longitudinal axis horizontal'and its traverse axis inclined at 45 to the horizontal. A Bunsen burner with a flame /2 inch to inch in height is placed under the free end of thespecimen'and adjusted sothat the flame tip is just in contact therewith. At the end of 30 seconds, the flame is removed and the specimen allowed to burn. A stop watch is started whenthe flame reaches the first mark, 1 inch from the end,=and-the time noted when the flame reachesthe 5-inch..mark. 111302186 the specimen does not continue: to burnafter the first ignition, the burner is placed under the free end for a secondperiod of 30 seconds immediately following the extinction of the flame. If the specimen does not continue to burn to the -inch mark after the second ignition, it is reported as self-extinguishing.

In ascertaining the resistance to discoloration, specimens are exposed to a light treatment and weatherometer test. The interval in hours before discoloration, amounting to a reduction in light reflectance, is regarded as the measure of resistance.

For the light test to determine yellowing and fading, a specimen is exposed to a sunlamp until a stage is reached where the decrease in light reflection is 10% according to the procedure of ASTM Designation D620-49.

This procedure is used to evaluate the relative resistance of the resinous composition to change in color when exposed to sunlight.

A description of the apparatus employed follows:

Lamp-A General Electric Sunlamp, Model BM 12, with reflector approximately inches in diameter.

DiscA phonograph turntable operating at 33 R. P. M. 17-inch diameter disc with suitable mounting rack.

Test specimen2 inches by 1 inch by 4; inch mounted flat on a table with long direction pointing in toward center of table and with the place of the sample 5 inches from the bottom of the bulb. Test temperature is 55 C. to 60 C.

The weatherometer test, wherein the specimen is exposed to alternate periods of heating and concurrent heating and wetting, is made according to the following procedure:

A test specimen 2% inches by 6 inches by inch is mounted in a suitable apparatus equipped with a carbon arc lamp and water spray. A circular rack 30 inches in diameter, which holds the specimens, rotates around the carbon arc lamp at 1 R. P. M. providing uniform distribution of the radiation on all specimens. A decrease in light reflectance of 10% is recorded as failure of the specimen.

Adequate ventilation is provided in the test chamber to prevent contamination of the specimens from products of combustion of the arc.

The apparatus employed in this test has the following specifications:

Line voltage 1 208-250 volts. Arc volts 120-145 volts. Arc current 15-17 amps.

/2 by 12 neutral cored upper; /z" by 4" neutral cored upper.

A globe of optical heat-resistant glass with cutofi at 2750 angstroms with an increase in transmission to 91% at 3700 angstroms.

Water is arranged to strike the test specimens in the form of a fine spray equally distributed over the specimens under the following operating conditions: 102 min. of light, 18 min. of light and water, temperature 145 F.i5 F., black panel temperature.

In order that the inventive concept herein disclosed may be more fully understood, examples are given by way of illustration only and any specific enumeration of details should not be interpreted as a limitation, except as expressed in the appended claims. All parts are parts by weight unless otherwise indicated.

EXAMPLE 1 92.5 parts of ethylene glycol, 67.0 parts of maleic anhydride and 265 parts of hexachloroendomethylene tetrahydrophthalic acid are charged into a suitable reaction vessel equipped with mechanical stirrer, thermometer, inlet and outlet tubes. The batch is heated under an inert atmosphere of carbon dioxide at a temperature of 145 C. to 155 C. until an acid number of 150 to 160 is Carbon electrodes hot reaction mixture and the temperature is raised to 160 C. to 120 C. and styrene is added in amounts of about 25% to about 75% by weight of the polyester reacu'on product. The mixture is then cooled to C. to 60 C. and the alkaline metal-organic acid salt stabilizer is added in the followingmanner: Mixed barium laurate and cadmium laurate in the ratio of' 3:2, respectively, so as to provide a content of 3% by weight of, the polyesterstyrene mixture is made into a 40% paste by first mixing the salt with a portionof the polyester-styrene mixture and then adding this pasteto the main portion of the resin with vigorous mixing. Mixing is continued until the mass exhibits a uniform, slightly hazy appearance and no particles large enough to be visible to the eye are evident in the resin. The resin is not filtered after addition of stabilizer, as this apparently removes part of the .stabilizer and results in a resin of relatively poorer color stability. The resin is then cooled below 40 C. and 1% by weight based on the total resin of ultraviolet absorber, Z-hydroxy, 4-methoxy benzophenone, is added as a 25 solution in styrene. In order that the final alkyd-styrene ratio'for this resin may have a ratio of 72:28, respectively, the initial cut of 75% polyester to 25 styrene monomer is used, so that the styrene added with the ultraviolet absorber will produce a final ratio of 78:28:1.5%, respectively.

Thefinal product has a Brookfield viscosity of 4.5 to 6.5 poises and a viscosity on the Gardner Holdt scale of between R and U (4.70 to 6.27 poises). The resinous composition has a stability exceeding five days at temperatures exceeding F. It has very good sunlight resistances, self-extinguishing characteristics, and low burning rate.

EXAMPLE 2 A resin is made according to the procedure of Example but without the barium-cadmium laurate stabiliz'er.

, The results obtained in testing the discoloration of the resins of Example 1, wherein the alkaline metal salt of organic acid is used as a heat stabilizer according to the teaching of the present invention and of Example 2, Where no heat stabilizer is employed are compared in Table 1. The heat and moisture resistance imparted to polyester-styrene compositions with other stabilizers is shown-by the data for Examples 3 through 11, set out in Table 1. The procedure and formulation employed is that of Example 1 with the exception of the stabilizer, which is that indicated in Table 1. Examples 3 through 7 illustrate the effect of employing stabilizers of the invention. Examples 7 through 11 illustrate the use of stabilizing compounds which fall outside the class of alkaline metal stabilizers contemplated by the teaching of the instant invention.

Table 1 Amount of Hours of Ex- Exemple Stabilizer Stabilizer, posure (Heat percent and Moisture) until Failure 1 Barium-Cadmium Laurate 3.0 1, 400

(8:2 ratio). 0 200 Barium laurate 3. 0 060 Cadmium laurate 3. 0 500 Barium-Cadmium stearate. 3. 0 540 Cadmium Octoate 3.0 710 Barium-Cadmium myristata- 3.0 560 Dlbutyl ttn Maleate 3.0 260 Lead stearate 3. 0 Dibasic lead stearate 3. 0 270 Trlaryl Phosphate 3. 0 140 The foregoing results demonstratethat discoloration is markedly improved when the st'abilizers'of the present invention are incorporated into the resins. The results obtained are particularly impressive when his considered that under the rigorous conditions of the testing procedures employed, each hour of increase in resistance is indicative of improved outdoor durability. A further advantage of the resinous compositions using the alkaline metal-organic acid salt stabilizers of the instant invention resides in the improvement in gloss-retention properties of these materials; After a 3-month-outdoor exposure, the improvement in gloss of the composition of Example 1 over that of Example 2 was approximately 20%.

We claim:

1. A clear, flame-resistant self-extinguishing resinous composition-resistant to discoloringefi'ects of--heat and light, comprising the reaction product of 1) a-polymerizable ethylenically unsaturated. polycarboxylic acid-polyhydric alcohol-alkylrphosphate polyester obtained as the reactionproduct' of a polyhydric alcoholand an ethylenicallyunsaturated polycarboxylic acid wherein said polyester contains-a halogenated member selected from the groupzconsisting-ofa halogenated polyhydric alcohol and a,halogenated polycarboxylic acid in'whi'ch the halo group is a member of the group consisting-of chlorine, bromine and iodine and is present inaan amount to yield from about.5% to about 50%- by weight-of said product and an alkyl phosphatewherein the alkyl group contains from 1-to 4 carbon atoms and is present in an amount to yield from about 0.1% to about-5% by weight ofsaid product, (2 a polymer'izablemonomer containing a-polymerizable CH =C group and ,having a boiling pointv of at least 60 C.,' (3) from 0.1% to'10%- based on the total weight of (1) and ('2) of-.an. alkaline earth metalsalt of fatty oilacids havingtfrorn 8 {[0120 carbon atoms, (4) from about 0.01% to about 5 by weight based onthe total weight of (1).- and (2) oi acompound having the general formula wherein' R is. analkyl. group having from :16 '4' carbon atoms, X1is a member selected-froth thegro'up consisting of hydrogen, halo groups, alk'yl' groupshaving from 1.to 4 carbonvatoms and alkoxyg-roups having-ffrom .l to 4 carbon atoms and Y is a member selected from the group consisting of hydrogen, hydroxyli groups, halo groups,,alky1 groups havingfroml to'4' carbon atoms and alkoxy groups having'fror'n 1 to 4 carbon atoms, and. (5.) an organic polymerization catalyst selected from the group consistingtof organic, peroxides and organic. ozonides.

2. A clear, flame resistant self-extinguishing resinous composition resistant to discoloringeflfects of heat and light comprising the reaction product of(1)' a polymerizable ethylenically unsaturated polycarboxylic acid-polyhydric alcohol-alkyl phosphate polyester obtainedas the 7 reaction product of a polyhydric alcohol and anjethylenically unsaturated polycarboxylic acid wherein said polyester contains a halogenated member selected from the group'consistingof a halogenated polyhydric alcohol and a halogenated,polycarboxylic acid in which the halogroup is a member of the group consistingof chlorine, bromine andfiodine and is present in anamount to yield from about 25% to about 35% by weight of said product and an alkyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about Q.5% to about 1.5% by weight of said product (2) Iapolyrnerizable monomer containing'a polymerizable CH=C group and having a boiling point of at least C., (3) from about 1% to about5% based on the total 'weight of (1) and (2) of an alkaline earth metal salt'of fa'tty oil acids having froin8 to 20 carbon atoms,

4) from about 0.1% to about 2% by weight based on thefltotal weight of ('1) and"(2')-of a'compound having the general-formulawherein R is an alkyl group h'avin'g from 1 to 4 carbon atom, X is am'ernber *seleetedffrom' the group consisting of hydrogen; halo group's, a1l yl--- groups having from 1 to 4 carbon atoiiis afid alk xy-groupsf having fromil to "4 *Y is a m'emberselected" from the group *corisistihg :QE hYd-rogen;--hydroxyl-' groups, halo reu'p's; alkyl roups Having from 1 t'o'-' 4 carbon atoms and-alkoxy-grot tps havingfrom: 1- to 4 carbon atoms, and (5 l organic peroxide polyineri-z'atioiicatalyst.

3l' clear; fliifne es'iStantfselflextinguishing resinous comp'osition'resistant to-thediscoloringelfects of heat and light' compiis'ing tll -reactionproduct of (1)' a polymerizable ethyleni'dall unsaturated polycarboxylic acid-polyhydric; alcohol'alkyl?phosphate polyester 1 obtained as the reaction product"oia pol'yhydricalcohol and an ethylenically' unsaturated polycarboxylic acid wherein said polyester containsa"halogenated*metnberselected from the group consisting of '-a*-halogenated polyhydric alcohol and a halogenated"polycarboxylicacid in which thehalo group is a member of 'the gr upconsisting of chlorine, bromine and iodine andispresentin anamount to yield from about "5 to"50 byweightof-said product and an alkyl phosphate wliere'in th alk'yl' group contains from 1 to 4 carbon atoms and is present-in an-amount to yield product, (2 )a polymerizable monom'er containing 'a polymerizable CH=C groiip andihaving a boiling point of at Iea'st 60"Ci; (3-) .fr or'n ffld to -10-% based on the total"'we ight'j-of (1)- and (2) of an alkalineearth' metal salt' of fatty oil acids haying frorriS to 20 carbon atoins, (4) from about 0.01% -to 5'% -by'-'weight based on'the total weight of 2-hydroxy-4-methoxybenzophenone, and (5) an organic peroxide polymerization catalyst.

4. A clear, flame-resistant selfi-extinguishing resinous composition resistantto the discoloring,,eflects of heat and light comprising .the reaction product of (1) a polymerizable ethyleni'cally unsaturated polycarboxylic acidpolyhydric alcohol-alkyl phosphate polyester obtained as the reaction product of a polyhydric alcohol and an ethyleni'cally unsaturated polycarboxylic acid wherein said polyester containszaf-halogenated merribei selected: from the groupconsis'tingi of a halogenated I polyhydric alcohol and a halogenatedepolycarboxylic acid in which the halo group is a membert' of the group'consistin'g of rchlorine', bromine and: iodine and is ''-present in'an amount to yield from about 25'% "to' 35% *by weightrof said product-and an alkyl phosphate wherein-the alkyl-1 group contains from 1 to 4'carbon at0rns andaispre'sent in an'arnount to yield from' about0.5%"to ab'out phosphorus by weight of said'product," (2)1 apolymeiizable monom'er containing a polymerizable CH =C group and havingza boiling point ofi'at'least6'0 C.,--'(3') fromi1'% to -5%- based onthe total weight of ('1): and" ('2) of -.analkalinev earth 'metal salt of fatty'oil-acids havingzfrom 8 toi20Icarbon atoms, (4) from: about-0.1% to about 2% b'yr" weight based on the" total weight of I 2+hydroxy=4 methoxybenzophenone, and (5 -'an organic peroxide polymerizationcatalyst.

5; A clear; fia'me' re'sistantself-extinguishing resinous composition resistant to: the discoloring effects of heat andlight comprising:the reactionproduct of (1) a polymerizable-ethyleni'callfi unsaturated polycarboxylic acidpolyhydric alcohol-a'lkyliphosphate:polyester obtained as the reaction product of a 'polyhydiic alcohol and an ethylenically unsaturated polycarboxylic acid wherein said polyester: contains a halogenat'e'd 'member selected from the group consisting of? a halogenated polyhydric alcohol and a halogenated polycarboxylic acidingwhicli the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in anamount to yield from about 25% to about 35% by weight of said product and triethyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.5 to about 1.5% phosphorus by weight of said product, (2) a styrene having a boiling point of at least 60 0., (3) from about 1% to about based on the total weight of (1) and (2) of a mixed salt of barium laurate and cadmium laurate, (4) from about 0.1% to about 2% by weight based on the total weight of 2-hydroxy-4-methoxybenzophenone, and (5) an organic peroxide polymerization catalyst.

6. A method for producing a clear, flame-resistant selfextinguishing resinous composition resistant to the discoloring efiects of heat and light which comprises preparing a polymerizable composition comprising 1) a polymerizable ethylenically unsaturated polycarboxylic acid-polyhydric alcohol-alkyl phosphate polyester obtained as the reaction product of a polyhydric alcohol and an ethylenically unsaturated polycarboxylic acid wherein said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 25% to about 35% by weight of said product and an alkyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.5% to about 1.5% by weight of said product and (2) a polymerizable monomer containing a polymerizable CH =C group and having a boiling point of at least 60 C.; thereafter intimately and rapidly blending therein from about 1% to 5% based on the total weight of (1) and (2) of an alkaline earth metal salt of an fatty oil acid having from 8 to 20 carbon atoms and from about 0.1% to about 2% by weight based on the total weight of (1) and (2) of a com pound having the general formula x o 1 ll R0 0 wherein R is an alkyl group having from 1 to 4 carbon atoms, X is a member selected from the group consisting of hydrogen, halo groups, alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having from 1 to 4 carbon atoms and Y is a member selected from the group consisting of hydrogen, hydroxyl groups, halo groups, alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having from 1 to 4 carbon atoms and contacting said polymerizable composition with an organic polymerization catalyst selected from the group consisting of organic peroxides and organic ozonides.

7. A method for producing a clear, flame-resistant self-extinguishing resinous composition resistant to the discoloring effects of heat and light which comprises preparing a polymerizable composition comprising (1) a polymerizable ethylenically unsaturated polycarboxylic acid-polyhydric alcohol-alkyl phosphate polyester wherein said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 25% to about 35% by weight of said product and an alkyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.5% to about 1.5% by weight of said product and (2) a polymerizable monomer 12 containing a polymerizable CH =C group and having a boiling point of at least 60 C.; thereafter intimately and rapidly blending therein from about 1% to 5% based on the total weight of (1) and (2) of a mixed barium-cadmium salt of a fatty oil acid having from 8 to 20 carbon atoms and adding thereto from about 0.1% to about 2% by weight based on the total weight of 1) and (2) of a compound having the general formula X 0 ag c) wherein R is an alkyl group having from 1 to 4 carbon atoms, X is a member selected from the group consisting of hydrogen, halo groups, alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having from 1 to 4 carbon atoms and Y" is a member selected from the group consisting of hydrogen, hydroxyl groups, halo groups, alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having from 1 to 4 carbon atoms and contacting said polymerizable composition with an organic peroxide polymerization catalyst.

8. A method for producing a clear, flame-resistant selfextinguishing resinous composition resistant to the discoloring efiects of heat and light which comprises preparing a polymerizable composition comprising (1) a polymerizable ethylenically unsaturated polycarboxylic acid-polyhydric alcohol-alkyl phosphate polyester obtained as the reaction product of a polyhydric alcohol and an ethylenically unsaturated polycarboxylic acid wherein said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 25 to about 35% by weight of said product and an alkyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.5% to about 1.5% by weight of said product and (2) styrene; thereafter intimately blending therein about 3% by weight based on the total weight of (l) to (2) of a mixture of barium laurate and cadmium laurate in the weight ratio of 3:2, respectively; adding thereto from about 0.1% to about 2% by weight based on the total weight of 2-hydroxy-4-methoxybenzophenone and contacting said polymerizable composition with an organic polymerization catalyst selected from the group consisting of organic peroxides and organic ozonides.

9. A clear, flame-resistant self-extinguishing resinous composition resistant to discoloring eifects of heat and light comprising the polymerizable mixture of (1) a polymerizable ethylenically unsaturated polycarboxylic acidpolyhydric alcohol-alkyl phosphate polyester obtained as the reaction product of a polyhydric alcohol and an ethylenically unsaturated polycarboxylic acid wherein said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 5% to about 50% by weight of said product and an alkyl phosphate wherein the alkyl group contains from ,1 to 4 carbon atoms and is present in an amount to yield from about 0.1% to about 5% by weight of said product, (2) a polymerizable monomer containing a polymerizable CH =C group and having a boiling point of at least 60 C., (3) from about 0.1% to about 10% based on the total weight of 1) and (2) of an alkaline earth metal salt of fatty oil acids having from 8 to 20 carbon atoms, (4) from about 001% to about 5% by weight based on the total weight of (1) and (2)-- of'a lig ht stabilizing compound having -the-general formula wherein R is, an .alkyl group having flOnDrl to 14 carbon atoms, X ,is. a member selectedirfromi the :group consisting of hydrogen, halo groups, alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having from 1 to 4 carbon atoms and Y is a member selected from the group consisting of hydrogen, hydroxyl groups, halo groups, alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having from 1 to 4 carbon atoms, and a polymerization inhibitor for said mixture.

10. A clear, flame-resistant self-extinguishing resinous composition resistant to the discoloring efliects of heat and light comprising the polymerizable mixture of (1) a polymerizable ethylenically unsaturated polycarboxylic acid-polyhydric alcohol-alkyl phosphate polyester obtained as the reaction product of a polyhydric alcohol and an ethylenically unsaturated polycarboxylic acid wherein said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 25% to about 35% by weight of said product and an alkyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.5% to about 1.5% phosphorus by weight of said product, (2) styrene, (3) from 1% to 5% of an alkaline earth metal salt of fatty oil acids having from 8 to 20 carbon atoms, (4) from about 0.1% to about 2% by weight based on the total weight of (1) and (2) of a compound having the general formula wherein R is an alkyl group having from 1 to 4 carbon atoms, X is a member selected from the group consisting of hydrogen, halo groups, alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having from 1 to 4 carbon atoms and Y is a member selected from the group consisting a hydrogen, hydroxyl groups, halo groups, alkyl groups having from 1 to 4 carbon atoms and alkoxy groups having from 1 to 4 carbon atoms, and (5) a polymerization inhibitor for said mixture.

11. A clear, flame-resistant self-extinguishing resinous composition resistant to the discoloring efiects of heat and light comprising the polymerizable mixture of (1) a polymerizable ethylenically unsaturated polycarboxylic acid-polyhydric alcohol-alkyl phosphate polyester obtained as the reaction product of a polyhydric alcohol and an ethylenically unsaturated polycarboxylic acid where said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 5% to 50% by weight of said product and an alkyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.1 to about 5% phosphorus by weight of said product, (2) styrene, (3) from about 0.1% to about based on the total weight of (l) and (2) of an alkaline earth metal salt of fatty oil acids having from 8 to carbon atoms, (4) from about 0.01% to '14 o about 5%} by" weight 'ba's ed on; the -roar weight-05 2'- hydroxy-4-methoxybnzdphenone; and (-5 a wr -meme tion inhibitor for said mixtlirefi' 4 12. 'A clear, flame resistant 'selfgextinguishing resinous compositionresistant -to the discoloring eflects of heat and'light comprising*the -polymerizable mixture" of (1) a polymerizable ethylenigally unsaturated polycarboxylic acid-polyhydric 'alcohol alk"l phosphate-polyester obtained asthe reactionproduct' 'of" a polyhydric alcohol and an ethylenically unsaturatedpolycarboxylic acid wherein said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 25% to about 35% by weight of said product and an alkyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.5 to about 1.5 phosphorus by weight of said product, (2) styrene, (3) from 1% to 5% of an alkaline earth metal salt of fatty oil acids having from 8 to 20 carbon atoms, (4) from about 0.1% to about 2% by weight based on the total weight of 2-hydroxy-4-methoxybenzophenone, and (5) a polymerization inhibitor for said mixture.

13. A clear, flame-resistant self-extinguishing resinous composition resistant to the discoloring effects of heat and light comprising the polymerizable mixture of (1) a polymerizable ethylenically unsaturated polycarboxylic acid-polyhydric alcohol-alkyl phosphate polyester obtained as the reaction product of a polyhydric alcohol and an ethylenically unsaturated polycarboxylic acid wherein! said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 25% to about 35% by Weight of said product and a triethyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.5% to about 1.5% phosphorus by weight of said product, (2) styrene, (3) from 1% to 5% based on the total weight of (1) and (2) of a barium-cadmium salt, (4) from about 0.1% to about 2% by weight based on the total weight of 2-hydroxy-4-methoxybenzophenone, and (5) a polymerization inhibitor for said mixture.

14. A clear, flame-resistant self-extinguishing resinous composition resistant to the discoloring effects of heat and light comprising the polymerizable mixture of (1) a polymerizable ethylenically unsaturated polycarboxylic acid-polyhydric alcohol-alkyl phosphate polyester obtained as the reaction product of a polyhydric alcohol and an ethylenically unsaturated polycarboxylic acid wherein said polyester contains a halogenated member selected from the group consisting of a halogenated polyhydric alcohol and a halogenated polycarboxylic acid in which the halo group is a member of the group consisting of chlorine, bromine and iodine and is present in an amount to yield from about 25% to about 35% by weight of said product and an alkyl phosphate wherein the alkyl group contains from 1 to 4 carbon atoms and is present in an amount to yield from about 0.5% to about 1.5% phosphorus by weight of said product, (2) styrene, (3) from 1% to 5% based on the total weight of (1) and (2) of barium laurate and cadmium laurate in the relative weight ratios of 3:2, respectively, (4) from about 0.1% to about 2% by weight based on the total weight of 2- hydroxy-4-methoxybenzophenone, and (5 as a polymerization inhibitor for said mixture, a small but effective amount of hydroquinone.

15. A clear, flame-resistant self-extinguishing resinous composition resistant to the discoloring efiects of heat and light comprising the polymerizable mixture of (1) ethylene glycol, maleic anhydride, hexachloroendomethyl 2,822,340 16 eue tetrahydrophthalic acid in amounts to yield from 0.008% by weight based on the total weight of the resinabout 25% to 35% chlorine by weight ofjsaidv product, ous composition of hydroquinone. and triethyl phosphate in an amount to yield from about 0.5% to about 1.5% phosphorus by weight of said prod- References Cited in the file of this Patent net, (2) styrene, (3) from 1% to 5% based on the total 5 a weight of (1) and (2) of barium laurate and cadmium UNITED STATES PATENTS laurate in the relative weight ratios of 3:2, respectively, 2,075,543 Reed-6t 30, 1953 4 from about 0.1% to about 2% by weight based on 2,669,544 Lowe 16, 1954 the total weight of 2-hydroxy-4-methoxybenzophenone, 2,669,548' Darby 15,1954

and (5) as a polymerization inhibitor for said mixture, 10 2,671,054 Coweu 1954 

1. A CLEAR, FLAME-RESISTANT SELF-EXTINGUISHING RESINOUS COMPOSITION RESISTANT TO DISCOLORING EFFECTS OF HEAT AND LIGHT, COMPRISING THE REACTION PRODUCT OF (1) A POLYMERIZABLE ETHYLENICALLY UNSATURATED POLYCARBOCYLIC ACID-POLYHYDRIC ALCOHOL-ALKYL PHOSPHATE POLYESTER OBTAINED AS THE REACTION PRODUCT OF A POLYHYDRIC ALCOHOL AND AN ETHYLENICALLY UNSATURATED POLYCARBOXYLIC ACID WHEREIN THE POLYESTER CONTAINS A HALOGENATED MEMBER SELECTED FROM THE GROUP CONSISTING OF A HALOGENATED POLYHYDRIC ALCOHOL AND A HALOGENATED POLYCARBOXYLIC ACID IN WHICH THE HALO GROUP IS A MEMBER OF THE GROUP CONSISTING OF CHLORINE, BROMINE AND IODINE AND IS PRESENT IN AN AMOUNT TO YIELD FROM ABOUT 5% TO ABOUT 50% BY WEIGHT OF SAID PRODUCT AND AN ALKYL PHOSPHATE WHEREIN THE ALKYL GROUP CONTAINS FROM 1 TO 4 CARBON ATOMS AND IS PRESENT IN AN AMOUNT TO YIELD FROM ABOUT 0U9% TO ABOUT 5% BY WEIGHT OF SAID PRODUCT, (2) A POLYMERIZABLE MONOMER CONTAINING A POLYMERIZABLE CH2=C< GROUP AND HAVING A BOILING POINT OF AT LEAST 60* C., (3) FROM 0.1% OF 10% BASED ON THE TOTAL WEIGHT OF (1) AND (2) OF AN ALKALINE EARTH METAL SALT OF FATTY OIL ACIDS HAVING FROM 8 TO 20 CARBON ATOMS, (4) FROM ABOUT 0.01% TO ABOUT 5% BY WEIGHT BASED ON THE TOTAL WEIGHT OF (1) AND (2) A COMPOUND HAVING THE GENERAL FORMULA 